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Spin crossover in polyaniline

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Abstract

Solutions of the basic form of polyaniline in m-cresol were studied by ESR and optical spectroscopy in the visible region. m-Cresol can slowly (during one month) protonate polyaniline. For the first time characteristic features of spin crossover were found: sharp changes in the magnetic susceptibility and the ESR line width of polyaniline at ∼200 and 250 K, a smooth decrease in the susceptibility and absorption with the temperature increase from 293 to 423 K, and the temperature hysteresis. The temperature-induced structural rearrangements of polyaniline are caused, most likely, by singlet-triplet transitions in relatively short sections of the polymer chain. The model of short sections permits to explain the origin of the temperature-independent part of susceptibility. Quantum-chemical calculations for the aniline dimers and tetramers describe correctly the singlet-triplet splitting value, thermochromism, and HFS constants in the spectrum of polyaniline.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 1 prosp. Akad. Semenova, 142432, Chernogolovka, Moscow Region, Russian Federation

    A. V. Kulikov, A. S. Komissarova, A. F. Shestakov & L. S. Fokeeva

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  1. A. V. Kulikov
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  2. A. S. Komissarova
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  3. A. F. Shestakov
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  4. L. S. Fokeeva
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Correspondence to A. V. Kulikov.

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Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1959–1966, October, 2007.

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Kulikov, A.V., Komissarova, A.S., Shestakov, A.F. et al. Spin crossover in polyaniline. Russ Chem Bull 56, 2026–2033 (2007). https://doi.org/10.1007/s11172-007-0316-5

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  • DOI: https://doi.org/10.1007/s11172-007-0316-5

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